Chloranil → 19-Hydroxy-4,6-androstadiene-3,17-dione

HRID 1834989Notes

Reaction equation

HRID 1834989 reaction equation
[OH:1][CH2:2][C@@:3]12[C@@H:20]3[C@H:11]([C@H:12]4[C@@:16]([CH2:18][CH2:19]3)([CH3:17])[C:15](=[O:21])[CH2:14][CH2:13]4)[CH2:10][CH2:9][C:8]1=[CH:7][C:6](=[O:22])[CH2:5][CH2:4]2.C1(Cl)C(=O)C(Cl)=C(Cl)C(=O)C=1Cl>C(O)(C)(C)C>[OH:1][CH2:2][C@@:3]12[C@@H:20]3[C@H:11]([C@H:12]4[C@@:16]([CH2:18][CH2:19]3)([CH3:17])[C:15](=[O:21])[CH2:14][CH2:13]4)[CH:10]=[CH:9][C:8]1=[CH:7][C:6](=[O:22])[CH2:5][CH2:4]2

Participants

4

Reactant 2

HCID 8371ChloranilHCID 25237919-Hydroxyandrostenedione

Product 1

HCID 5428584419-Hydroxy-4,6-androstadiene-3,17-dione

Reagents, catalysts & solvents 1

HCID 6386tert-ButanolSolvent

Procedure

19-Hydroxy-4-androstene-3,17-dione and chloranil are dissolved in t-butanol which is rapidly brought to its reflux temperature. The t-butanol is removed by distillation at atmospheric pressure at such a rate that the reflux time and distillation time approximate one hour. The dark pasty residue is triturated with hot chloroform and cooled. The solid residue is removed by filtration and the filtrate extracted with water, followed by a 2% sodium hydroxide solution, washed with water, dried over magnesium sulfate and the solvent removed under vacuum to yield 19-hydroxy-4,6-androstadiene-3,17-dione. The diene so obtained is dissolved in acetone and chilled in an ice bath. Jones reagent is added over a period of 10 minutes and stirring continued for an additional 45 minutes. The mixture is poured onto water. The solid which separates is filtered and recrystallized from benzene to yield 4,6-androstadiene-3,17,19-trione.

Workup

  1. temperaturereflux temperature
  2. customThe t-butanol is removed by distillation at atmospheric pressure at such a rate
  3. distillationthat the reflux time and distillation time approximate one hour
  4. customThe dark pasty residue is triturated with hot chloroform
  5. temperaturecooled
  6. customThe solid residue is removed by filtration
  7. extractionthe filtrate extracted with water
  8. washwashed with water
  9. dry with materialdried over magnesium sulfate
  10. customthe solvent removed under vacuum

Sources & evidence

ORD record
ord-4d26a021625b47adba164795de982bdc
Source dataset
uspto-grants-1978_01
Patent number
US04071625

Reaction notes

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